Method of etching porous film

ABSTRACT

A method of etching a porous film is provided. The method includes supplying a first gas into a processing chamber of a plasma processing apparatus in which an object to be processed including a porous film is accommodated, and generating a plasma of a second gas for etching the porous film in the processing chamber. The first gas is a processing gas having a saturated vapor pressure of less than or equal to 133.3 Pa at a temperature of a stage on which the object is mounted in the processing chamber, or includes the processing gas. In the step of supplying the first gas, no plasma is generated, and a partial pressure of the processing gas which is supplied into the processing chamber is set to be greater than or equal to 20% of the saturated vapor pressure.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to Japanese Patent Application No.2015-085878 filed on Apr. 20, 2015, the entire contents of which areincorporated herein by reference.

TECHNICAL FIELD

Embodiments of the disclosure relate to a method of etching a porousfilm.

BACKGROUND ART

In an electronic device such as a semiconductor device, a porous filmmay be used. As the porous film, for example, a film formed of a lowdielectric constant material such as a SiOC film is used. Inmanufacturing of such an electronic device, a process is performed inwhich a fine pattern formed in a photoresist by lithography istransferred to a hard mask such as a TiN film, a SiO₂ film, or a Si₃N₄film by plasma etching, as necessary, and the pattern is subsequentlytransferred to the porous film.

In the plasma etching of the porous film, radicals are generated byexciting a gas for etching in a processing chamber of a plasmaprocessing apparatus. The radicals may enter pores of the porous film todamage the porous film. For this reason, there have been proposed sometechnologies for protecting the porous film from the radicals.

For example, Reference 1 (Liping Zhang et al., “Damage Free CryogenicEtching of a Porous Organosilica Ultralow-k Film”, ECS Solid State Lett.2013 volume 2, issue 2, N5-N7) describes a technology in which theporous film is etched under an extremely low temperature to condense areaction product in the porous film. In this technology, the reactionproduct condensed in the porous film restrains the radicals fromentering the porous film. In order to condense such a reaction product,a temperature at the time of etching the porous film is set to be lowerthan or equal to −70° C.

In addition, Reference 2 (Markus H. Heyne et al., “Quantitativecharacterization of pore stuffing and unstuffing for postporosity plasmaprotection of low-k materials”, Journal of Vacuum Science & TechnologyB32, 062202 (2014)) describes a technology in which the porous film ispermeated with a polymethylmethacrylate resin (PMMA), and the PMMArestrains the radicals from entering the porous film. In thistechnology, after the etching of the porous film is finished, the PMMAis removed by a plasma process using a mixed gas of a hydrogen gas and ahelium gas, or by a post-treatment such as laser annealing.

SUMMARY OF INVENTION Technical Problem

In the etching at an extremely low temperature as in the technologydescribed in Reference 1, it is impossible to use the plasma processingapparatus which includes a cooling mechanism using a usual coolingmedium, and it is necessary to use a plasma processing apparatus whichincludes a cooling mechanism using, for example, liquid nitrogen or thelike. Therefore, in this etching at an extremely low temperature, therunning cost increases. In addition, in the technology described inReference 2, a step of allowing the PMMA to permeate the porous film isnecessary, and a dedicated processing apparatus is necessary. Further,in the technology described in Reference 2, the porous film may bedamaged by the post-treatment for removing the PMMA.

Therefore, an improved method for etching a porous film which is capableof reducing damage of the porous film is necessary.

Solution to Problem

In one aspect, a method of etching a porous film is provided. The methodincludes (a) a step (hereinafter, referred to as a “pore sealing step”)of supplying a first gas into a processing chamber of a plasmaprocessing apparatus in which an object to be processed including aporous film is accommodated, and (b) a step (hereinafter, referred to asan “etching step”) of generating a plasma of a second gas for etchingthe porous film in the processing chamber. The first gas is a processinggas having a saturated vapor pressure of less than or equal to 133.3 Paat a temperature of a stage on which the object is mounted in theprocessing chamber, or includes the processing gas. In addition, in thepore sealing step, no plasma is generated, and a partial pressure of theprocessing gas supplied into the processing chamber is greater than orequal to 20% of the saturated vapor pressure. In one embodiment, apressure of a space in the processing chamber in the pore sealing stepis set to a pressure of less than or equal to 133.3 Pa (1 Torr). Inaddition, in one embodiment, a pressure of a space in the processingchamber in the etching step is set to a pressure less than or equal to40 Pa (300 mTorr). Furthermore, the pressure of the space in theprocessing chamber in the etching step may be set to be less than orequal to 13.33 Pa (100 mTorr).

In the method according to the one aspect, in order to seal pores of theporous film, the processing gas having a saturated vapor pressure ofless than or equal to 133.3 Pa at a stage temperature is used, and theprocessing gas is supplied into the processing chamber at the partialpressure which is less than or equal to 20% of the saturated vaporpressure. In the pore sealing step using the processing gas of such apartial pressure, the processing gas in the pores of the porous film isliquefied by capillary condensation, and the liquid in the poresrestricts radicals generated in the etching step from entering the poresof the porous film. The liquefaction may be performed at a temperaturewhich is available by a usual cooling mechanism of a plasma processingapparatus, for example, at a temperature of approximately −50° C., or ata temperature of higher than or equal to −50° C., instead of anextremely low temperature. In addition, the liquid generated by theliquefaction of the processing gas is vaporized, for example, by settingthe temperature of the object to be processed to ordinary temperature,and thus can be easily removed. Therefore, it is possible to protect theporous film from the radicals for etching, without using the coolingmechanism for adjusting the temperature of the object to be processed toan extremely low temperature, and it is possible to reduce damage of theporous film.

In one embodiment, a sequence including the pore sealing step and theetching step may be repeatedly performed. The liquid introduced into thepores of the porous film by the pore sealing step may vaporize duringthe etching step. According to this embodiment, the etching step isperformed for a period of time during which the protection of the porousfilm by the liquid is maintained, and the pore sealing step and theetching step are performed again. Accordingly, it is possible to ensurean etching amount while reducing damage of the porous film.

The method in one embodiment further includes a step (hereinafter,referred to as a “gas substituting step”) of supplying the second gasinto the processing chamber without generating a plasma between the poresealing step and the etching step. According to this embodiment, afterthe first gas in the processing chamber is replaced with the second gasby the gas substituting step, the plasma is generated. Therefore,generation of unnecessary active species is suppressed.

In one embodiment, the processing gas used in the pore sealing step maybe a fluorocarbon gas. In one embodiment, the processing gas includes atleast one of C₇F₈ gas and C₆F₆ gas, and the partial pressure of theprocessing gas supplied into the processing chamber in the pore sealingstep may be set to be less than or equal to 100% of the saturated vaporpressure.

In one embodiment, the processing gas used in the pore sealing step maybe a hydrocarbon gas. In one embodiment, the processing gas may be anoxygen-containing hydrocarbon gas. The processing gases of theseembodiments may be used in the pore sealing step. In one embodiment, thenumber of oxygen atoms in molecules included in the processing gas maybe less than or equal to ½ of the number of carbon atoms in themolecules. According to this processing gas, it is possible to liquefythe processing gas in the pores of the porous film while reducing damageof the porous film due to oxygen.

In one embodiment, the method may further include a step (hereinafter,referred to as a “removing step”) of exhausting a gas generated byvaporizing the liquid which is generated from the processing gas andexists in the porous film. In the removing step, the temperature of theobject to be processed including the porous film is set to be higherthan or equal to ordinary temperature (for example, 20° C.) in theprocessing chamber of the plasma processing apparatus which is used inthe pore sealing step and the etching step. Alternatively, in theremoving step, the temperature of the object to be processed includingthe porous film in a dedicated apparatus is set to be higher than orequal to ordinary temperature (for example, 20° C.). The dedicatedapparatus may by connected to the plasma processing apparatus used inthe pore sealing step and the etching step, via a vacuum transfersystem.

Advantageous Effects of Invention

As described above, the improved method for etching a porous film isprovided, and it becomes possible to protect the porous film from theradicals for etching, without using the cooling mechanism for adjustingthe temperature of the object to be processed to an extremely lowtemperature, and it becomes possible to reduce damage of the porousfilm.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a flowchart illustrating a method of etching a porous filmaccording to one embodiment.

FIG. 2 is a cross-sectional view illustrating an example of an object tobe processed.

FIG. 3 is a diagram schematically illustrating a plasma processingapparatus according to one embodiment.

FIG. 4 is a timing chart of an example relevant to the methodillustrated in FIG. 1.

FIGS. 5 to 9 are cross-sectional views illustrating states of the objectto be processed after performing respective steps of the methodillustrated in FIG. 1.

FIG. 10 is a graph illustrating a relationship between saturated vaporpressures of various fluorocarbon gases and the temperature of a stagePD.

FIG. 11 is a graph illustrating a relationship between a saturated vaporpressure of another example of the processing gas and the temperature ofthe stage PD.

FIG. 12 is a graph illustrating a refractive index obtained byExperimental Example 1.

FIGS. 13A and 13B are graphs each illustrating a result of an FTIRanalysis of a porous film after processing of Experimental Example 2, aporous film after processing of Experimental Example 3, and a porousfilm after processing of Comparative Experimental Example 1.

DESCRIPTION OF EMBODIMENTS

Hereinafter, various embodiments will be described in detail withreference to the drawings. Furthermore, the same reference numerals areapplied to the same or the corresponding parts in each of the drawings.

FIG. 1 is a flowchart illustrating a method of etching a porous filmaccording to one embodiment. A method MT illustrated in FIG. 1 is amethod of etching a porous film of an object to be processed. FIG. 2 isa cross-sectional view illustrating an example of the object to beprocessed. The object to be processed (hereinafter, may also be referredto as a “wafer W”) illustrated in FIG. 2 is provided with a substrateSB, a porous film PL, and a mask MK. The porous film PL is disposed onthe substrate SB. In the porous film PL, a plurality of pores is formed.The pores may have an average width of a few nm, for example, 1 nm to 2nm. It should be noted that the average width is an average value ofmaximum widths of the respective pores. In addition, the porous film isa film formed of a low dielectric constant material, such as a SiOCfilm. The porous film PL may be formed, for example, by a film formingmethod such as a CVD method or a spin film forming method.

The mask MK is disposed on the porous film PL. In one instance, the maskMK may include a first layer L1 and a second layer L2. For example, thefirst layer L1 may be a silicon oxide film, and the second layer L2 maybe a TiN film. In the mask MK, a pattern which is supposed to betransferred to the porous film PL is formed. For example, in the maskMK, a pattern having an opening is formed. Such a mask MK may be formedby using a lithography technology and plasma etching. The plasma etchingmay be performed in a series of steps of the method MT by using a plasmaprocessing apparatus 10.

In the method MT, prior to Step ST1, the wafer W is accommodated in aprocessing chamber of a plasma processing apparatus. FIG. 3 is a diagramschematically illustrating a plasma processing apparatus according toone embodiment. In FIG. 3, the structure in a vertical section of theplasma processing apparatus of an example which may be used forperforming the method MT is schematically illustrated. The plasmaprocessing apparatus 10 illustrated in FIG. 3 is a capacitive couplingplasma etching apparatus, and is provided with a processing chamber 12having an approximately cylindrical shape. An inner wall surface of theprocessing chamber 12, for example, is formed of aluminum to which ananodic oxidization treatment is applied. The processing chamber 12 isframe grounded.

On a bottom portion of the processing chamber 12, a support portion 14having an approximately cylindrical shape is disposed. The supportportion 14, for example, is formed of an insulating material. Thesupport portion 14 vertically extends in the processing chamber 12 fromthe bottom portion of the processing chamber 12. In the processingchamber 12, a stage PD is disposed. The stage PD is supported by thesupport portion 14.

The wafer W accommodated in the processing chamber 12 of the plasmaprocessing apparatus 10 is mounted on the stage PD, and the stage PDholds the wafer W. The stage PD includes a lower electrode LE and anelectrostatic chuck ESC. The lower electrode LE includes a first plate18 a and a second plate 18 b. The first plate 18 a and the second plate18 b, for example, are formed of metal such as aluminum, and have anapproximately disc shape. The second plate 18 b is disposed on the firstplate 18 a, and is electrically connected to the first plate 18 a.

On the second plate 18 b, the electrostatic chuck ESC is disposed. Theelectrostatic chuck ESC has a structure in which an electrode which is aconductive film is arranged between a pair of insulating layers orinsulating sheets. A direct current power source 22 is electricallyconnected to the electrode of the electrostatic chuck ESC via a switch23. This electrostatic chuck ESC attracts the wafer W by anelectrostatic force such as a Coulomb force which is generated by adirect current voltage from the direct current power source 22.Accordingly, the electrostatic chuck ESC is able to hold the wafer W. Aheater may be embedded in the electrostatic chuck ESC, and a heaterpower source disposed outside the processing chamber 12 may be connectedto the heater.

A focus ring FR is arranged on a peripheral portion of the second plate18 b to surround the edges of the wafer W and the electrostatic chuckESC. The focus ring FR is provided to improve etching uniformity. Thefocus ring FR is formed of a material which is suitably selecteddepending on a material of an etching target film, and for example, maybe formed of a material such as silicon and quartz.

A cooling medium flow path 24 is formed in the inside of the secondplate 18 b. The cooling medium flow path 24 constitutes a temperatureadjustment mechanism. A cooling medium is supplied to the cooling mediumflow path 24 from a chiller unit which is disposed outside theprocessing chamber 12 through a pipe 26 a. The cooling medium suppliedto the cooling medium flow path 24 returns to the chiller unit through apipe 26 b. Thus, the cooling medium is circulated between the coolingmedium flow path 24 and the chiller unit. By controlling the temperatureof the cooling medium, the temperature of the wafer W which is supportedon the electrostatic chuck ESC is controlled. As for the cooling medium,a general cooling medium which is capable of cooling the wafer W at atemperature of higher than or equal to −50° C. is used, for example. Assuch a cooling medium, Galden (registered trademark) is exemplified.

In addition, in the plasma processing apparatus 10, a gas supply line 28is provided. The gas supply line 28 supplies a heat transfer gas, forexample, He gas, from a heat transfer gas supply mechanism, between anupper surface of the electrostatic chuck ESC and a back surface of thewafer W.

In addition, the plasma processing apparatus 10 is provided with anupper electrode 30. The upper electrode 30 is arranged above the stagePD to face the stage PD. The lower electrode LE and the upper electrode30 are arranged to be approximately parallel with each other. Aprocessing space S for performing a plasma processing with respect tothe wafer W is provided between the upper electrode 30 and the lowerelectrode LE.

The upper electrode 30 is held at an upper portion of the processingchamber 12 through an insulating shielding member 32. The upperelectrode 30 may include an electrode plate 34 and an electrode holdingbody 36. The electrode plate 34 faces the processing space S, and aplurality of gas injection holes 34 a is formed in the electrode plate34. The electrode plate 34 is formed of a material such as silicon or asilicon oxide.

The electrode holding body 36 detachably holds the electrode plate 34,and may be formed of, for example, a conductive material such asaluminum. The electrode holding body 36 may have a water coolingstructure. In an inner portion of the electrode holding body 36, a gasdiffusion space 36 a is formed. From the gas diffusion space 36 a, aplurality of gas circulation holes 36 b extends downward to communicatewith the gas injection holes 34 a. In addition, a gas introduction port36 c for introducing a processing gas into the gas diffusion space 36 ais formed in the electrode holding body 36, and a gas supply pipe 38 isconnected to the gas introduction port 36 c.

A gas source group 40 (GSG) is connected to the gas supply pipe 38through a valve group (VG) 42 and a flow rate controller group (FCG) 44.The gas source group 40 includes a plurality of gas sources. Theplurality of gas sources includes one or more gas sources for supplyinga first gas and one or more gas sources for supplying a second gas. Inaddition, the plurality of gas sources of the gas source group 40 mayinclude a gas source for a gas which is used in Step ST4 of the methodMT to be described later, for example, argon or nitrogen gas.

The first gas includes a processing gas which is liquefied in the poresof the porous film PL. The first gas will be described later in detailin conjunction with the method MT. The second gas is a gas for etchingthe porous film PL. For example, the second gas may be a mixed gasincluding SiF₄ gas, NF₃ gas, and a rare gas such as Ar gas, or a mixedgas including CF₄ gas, O₂ gas, and a rare gas such as Ar gas.

The valve group 42 includes a plurality of valves, and the flow ratecontroller group 44 includes a plurality of flow rate controllers suchas a mass flow controller. Each of the gas sources of the gas sourcegroup 40 is connected to the gas supply pipe 38 via a correspondingvalve of the valve group 42 and a corresponding flow rate controller ofthe flow rate controller group 44.

In addition, a deposition shield 46 is detachably provided in the plasmaprocessing apparatus 10 along an inner wall of the processing chamber12. The deposition shield 46 is also disposed on the periphery of thesupport portion 14. The deposition shield 46 prevents an etchingby-product (a deposition) from being attached to the processing chamber12, and may be formed by coating an aluminum material with a ceramicsuch as Y₂O₃.

An exhaust plate 48 is disposed on a lower side of the processingchamber 12 and between the support portion 14 and a side wall of theprocessing chamber 12. The exhaust plate 48 may be formed, for example,by coating an aluminum material with a ceramic such as Y₂O₃. An exhaustport 12 e is provided under the exhaust plate 48 and in the processingchamber 12. An exhaust device 50 is connected to the exhaust port 12 ethrough an exhaust pipe 52. The exhaust device (ED) 50 includes a vacuumpump such as a turbo molecular pump, and is able to depressurize thespace in the processing chamber 12 to a desired degree of vacuum. Inaddition, a loading/unloading port 12 g of the wafer W is formed in theside wall of the processing chamber 12, and the loading/unloading port12 g can be opened and closed by a gate valve 54.

The plasma processing apparatus 10 further includes a first highfrequency power source 62 and a second high frequency power source 64.The first high frequency power source 62 is an electric power source forgenerating a high frequency power for plasma generation, and generates ahigh frequency power having a frequency of, for example, 27 MHz to 100MHz. The first high frequency power source 62 is connected to the upperelectrode 30 via a matching box (MB) 66. The matching box 66 is acircuit for matching an output impedance of the first high frequencypower source 62 with an input impedance of a load side (the upperelectrode 30 side). It should be noted that the first high frequencypower source 62 may be connected to the lower electrode LE via thematching box 66.

The second high frequency power source 64 is an electric power sourcefor generating a high frequency bias power for attracting ions to thewafer W, and generates a high frequency bias power having a frequencywithin a range of, for example, 400 kHz to 13.56 MHz. The second highfrequency power source 64 is connected to the lower electrode LE via thematching box (MB) 68. The matching box 68 is a circuit for matching anoutput impedance of the second high frequency power source 64 with aninput impedance of the load side (the lower electrode LE side).

In one embodiment, the plasma processing apparatus 10 is furtherprovided with a control unit Cnt. The control unit Cnt is a computerincluding a processor, a storage unit, an input device, a displaydevice, and the like, and controls each unit of the plasma processingapparatus 10. With the control unit Cnt, it is possible for an operatorto perform an input operation of a command or the like for managing theplasma processing apparatus 10 using the input device, and it ispossible to visually display an operational status of the plasmaprocessing apparatus 10 using the display device. Further, the storageunit of the control unit Cnt stores a control program for causing theprocessor to control various processes performed in the plasmaprocessing apparatus 10, or a program for causing each unit of theplasma processing apparatus 10 to perform processes according toprocessing conditions, that is, a processing recipe.

Referring back to FIG. 1, the method MT will be described in detail. Thefollowing description refers to FIGS. 4 to 9 in addition to FIG. 1. FIG.4 is a timing chart of an example relevant to the method MT. FIGS. 5 to9 are cross-sectional views illustrating states of the object to beprocessed after performing respective steps of the method MT. In FIG. 4,a high level (indicated by “H” in FIG. 4) of supply of the first gasindicates that the first gas is supplied into the processing chamber ofthe plasma processing apparatus, and a low level (indicated by “L” inFIG. 4) of supply of the first gas indicates that the first gas is notsupplied into the processing chamber of the plasma processing apparatus.In addition, a high level (indicated by “H” in FIG. 4) of supply of thesecond gas indicates that the second gas is supplied into the processingchamber of the plasma processing apparatus, and a low level (indicatedby “L” in FIG. 4) of supply of the second gas indicates that the secondgas is not supplied into the processing chamber of the plasma processingapparatus. In addition, a high level (indicated by “H” in FIG. 4) ofsupply of the high frequency power indicates that the high frequencypower is supplied from the first high frequency power source 62, andthus the plasma is generated, and a low level (indicated by “L” in FIG.4) of supply of the high frequency power indicates that the highfrequency power is not supplied from the first high frequency powersource 62, and thus the plasma is not generated.

In the method MT, first, Step ST1 is performed. In Step ST1, the firstgas is supplied into the processing chamber 12, in a state where thewafer W is mounted on the stage PD. In FIG. 4, it is illustrated thatthe first gas is supplied into the processing chamber 12 between time t1and time t2. In addition, in Step ST1, the pressure in the processingchamber 12 is set to a predetermined pressure by the exhaust device 50.Further, in Step ST1, the temperature of the stage PD is set to atemperature of higher than or equal to −50° C. In Step ST1, asillustrated in FIG. 4, the high frequency power is not supplied from thefirst high frequency power source 62. Therefore, in Step ST1, plasma isnot generated.

The first gas is the processing gas which is liquefied in the pores ofthe porous film PL, or includes the processing gas. The processing gasis a gas having a saturated vapor pressure of less than or equal to 1Torr (i.e. 133.3 Pa) at the temperature of the stage PD, for example, atemperature of higher than or equal to −50° C. The first gas is suppliedinto the processing chamber 12 such that the partial pressure of theprocessing gas is a partial pressure of greater than or equal to 20%.

In Step ST1, the processing gas of the first gas is liquefied in thepores of the porous film PL by capillary condensation. The capillarycondensation is a phenomenon in which condensation or liquefaction of agas occurs at a pressure lower than the saturated vapor pressure of thegas in a capillary. By the capillary condensation, even when the partialpressure of the processing gas is less than or equal to the saturatedvapor pressure, the processing gas entering in the pores of the porousfilm PL is liquefied in the pores and becomes a liquid. When Step ST1 isperformed, as illustrated in FIG. 5, a region SR is formed in the porousfilm PL, and in the region SR, the pores are filled with the liquidgenerated from the processing gas. The region SR extends over a rangefrom a top surface of the porous film PL to a certain depth. Forming theregion SR or filling the pores of the porous film PL by liquid enablesthat radicals generated by Step ST3 to be described later are restrictedfrom entering the pores of the porous film PL. As a result thereof,damage of the porous film PL is reduced. The type of processing gas, andvarious conditions of Step ST1 will be described later in detail.

In the method MT, the supply of the first gas into the processingchamber 12 is stopped at the completion time of Step ST1, andsubsequently, in one embodiment, Step ST2 is performed. In Step ST2, thesecond gas is supplied into the processing chamber 12. The second gas isformed of a mixed gas including SiF₄ gas, NF₃ gas, and a rare gas suchas Ar gas, or a mixed gas including CF₄ gas, O₂ gas, and a rare gas suchas Ar gas, and is also used in an etching process of Step ST3. In FIG.4, it is illustrated that the supply of the first gas is stopped at thetime t2 at which Step ST1 is terminated, the supply of the second gasinto the processing chamber 12 is started from the time t2, and Step ST2started at time t2 is continued until time t3. In addition, asillustrated in FIG. 4, the high frequency power is not supplied from thefirst high frequency power source 62 during a period of performing StepST2. Therefore, in Step ST2, plasma is not generated.

In Step ST2, the pressure in the processing chamber 12 is set to apredetermined pressure by the exhaust device 50. The predeterminedpressure is a pressure identical to the pressure in the processingchamber 12 at the time of performing Step ST3. In addition, in Step ST2,the temperature of the stage PD, that is, the temperature of the wafer Wis set to a temperature identical to the temperature of the stage PD atthe time of performing Step ST3, for example, a temperature of higherthan or equal to −50° C.

In Step ST2, the first gas in the processing chamber 12 is replaced withthe second gas without generating the plasma. Therefore, generation ofunnecessary active species, that is, active species derived from thefirst gas is suppressed.

In subsequent Step ST3, the plasma of the second gas is generated. Tothis end, in Step ST3, a state is maintained in which the second gas issupplied into the processing chamber 12, and the high frequency power issupplied from the first high frequency power source 62. In FIG. 4, it isillustrated that the high frequency power is supplied from the firsthigh frequency power source 62 during a period of performing Step ST3,that is, during a period from the time t3 to time t4. In addition, inStep ST3, the pressure in the processing chamber 12 is set to apredetermined pressure by the exhaust device 50. The predeterminedpressure is a pressure of, for example, less than or equal to 300 mTorr(40 Pa). The predetermined pressure may be a pressure of less than orequal to 100 mTorr (13.33 Pa). In addition, in Step ST3, the temperatureof the stage PD is set to a temperature of, for example, higher than orequal to −50° C. In Step ST3, the high frequency bias power may besupplied from the second high frequency power source 64 to the lowerelectrode LE.

In Step ST3, the porous film PL is etched by the active species, forexample, the radicals. Accordingly, as illustrated in FIG. 6, the porousfilm PL is etched in a portion exposed through the mask MK. Asillustrated in FIG. 6, a region in which the porous film PL is etched inStep ST3 is a region shallower than the region SR with respect to thetop surface of the porous film PL. That is, as illustrated in FIG. 6,the region SR remains by a certain depth (depth X) from a top surface ofthe porous film PL, after performing Step ST3.

When Steps ST2 and ST3 described above are performed for a long periodof time, supply of the second gas makes the partial pressure of theprocessing gas of the first gas existing in the processing chamber belower than or equal to the saturated vapor pressure. Therefore, theprocessing gas entering in the pores of the porous film PL and thenliquefied is vaporized again, and is discharged to the outside of thepores. That is, the liquid in the pores of the porous film PL isvaporized, and the porous film PL is in a state in which the radicalsare able to enter the pores. For this reason, in one embodiment, asequence SQ including Step ST1, Step ST2, and Step ST3 is repeatedlyperformed. That is, Step ST1 is performed, and thus, as illustrated inFIG. 7, the region SR is formed again in a range from the top surface ofthe porous film PL to a certain depth. Subsequently, Step ST2 isperformed, and thus the first gas in the processing chamber 12 isreplaced with the second gas. Subsequently, Step ST3 is performed, andthe porous film PL is etched again, as illustrated in FIG. 8.Accordingly, the sequence SQ can be performed again until a protectiveeffect by the liquid in the porous film PL is diminished, and thus it ispossible to protect the porous film PL from the radicals, while ensuringthe etching amount of the porous film PL.

In the method MT of one embodiment, in Step STJ, it is determinedwhether or not stop conditions are satisfied. When the number of timesof performing the sequence SQ reaches a predetermined number of times,it is determined that the stop conditions are satisfied. In Step STJ,when it is determined that the stop conditions are not satisfied, thesequence SQ is performed again. In contrast, in Step STJ, when it isdetermined that the stop conditions are satisfied, the performing of thesequence SQ is terminated, and the process proceeds to Step ST4.

In Step ST4, a treatment is performed in which the liquid in the poresof the porous film PL is vaporized to generate the gas and exhaust thegenerated gas. Step ST4 of one embodiment may be performed in the plasmaprocessing apparatus 10. In this embodiment, the temperature of thestage PD is set to a temperature at which the liquid in the pores isable to be vaporized. For example, the temperature of the stage PD isset to a temperature of higher than or equal to ordinary temperature(for example, 20° C.). In addition, in Step ST4, argon gas is suppliedinto the processing chamber 12, and the pressure in the processingchamber 12 is set to a predetermined pressure, for example, 0.1 Torr(13.33 Pa) by the exhaust device 50. In Step ST4, the liquid in thepores of the porous film PL is vaporized and becomes the gas, and thegas is exhausted from the space in the processing chamber 12 by theexhaust device 50. Accordingly, the liquid in the pores of the porousfilm PL is removed.

In Step ST4 of another embodiment, the wafer W may be placed under atemperature environment in which the liquid in the pores is able to bevaporized in another processing apparatus connected to the plasmaprocessing apparatus 10 via a vacuum transfer system.

As illustrated in FIG. 9, performing such a method MT allows the patternof the mask MK to be transferred to the porous film PL while damage ofthe porous film PL is reduced. In addition, according to the method MT,Step ST1, Step ST2, and Step ST3 can be performed by using a singleplasma processing apparatus 10. Furthermore, in one embodiment, Step ST4in addition to Step ST1, Step ST2, and Step ST3 can be performed byusing the single plasma processing apparatus 10.

Hereinafter, the processing gas used in Step ST1, and the variousconditions of Step ST1 will be described.

A first example of the processing gas is a fluorocarbon gas. FIG. 10 isa graph illustrating a relationship between saturated vapor pressures ofvarious fluorocarbon gases and the temperature of the stage PD.“1000/temperature” on a horizontal axis of the graph of FIG. 10indicates a value which is obtained by dividing 1000 by the temperatureof the stage PD, and a vertical axis indicates a log₁₀ (saturated vaporpressure (mTorr)). Plots illustrated in FIG. 10 are actual measuredvalues showing the relationship between the saturated vapor pressures ofthe various fluorocarbon gases and the temperature of the stage PD. Asillustrated in FIG. 10, a plurality of actual measured values eachshowing the relationship between the saturated vapor pressure of eachfluorocarbon gas and the temperature of the stage PD are positioned onan approximately straight line in the graph of FIG. 10.

It is known that the saturated vapor pressure is well-approximated by anexperimental equation referred to as an Antoine Equation of thefollowing Equation (1). In Equation (1), A, B, and C are constant valuesdetermined depending on a substance, T is an absolute temperature, and pis the saturated vapor pressure.

$\begin{matrix}{{\log_{10}p} = {A - \frac{B}{T + C}}} & (1)\end{matrix}$

A relationship between the saturated vapor pressure p and the absolutetemperature T which is defined by the Antoine Equation of Equation (1)is a linear relationship in the graph illustrated in FIG. 10. It shouldbe noted that, when the constant value C is not zero, the straight lineillustrated in FIG. 10 is just shifted to a horizontal direction, andthus the linear relationship still exists in the relationship betweenthe saturated vapor pressure p and the absolute temperature T.Therefore, a relationship of a plurality of actual measured valuesrelevant to each fluorocarbon gas illustrated in FIG. 10 is identical tothe linear relationship defined by the Antoine Equation. Accordingly, itis possible to quantitatively predict a saturated vapor pressure in atemperature region having no actual measured value, by using thestraight line extrapolated from the actual measured values.

As can be seen from the actual measured values shown in FIG. 10 or thestraight line which is extrapolated on the basis of the actual measuredvalues, the C₇F₈ gas and the C₆F₆ gas have a saturated vapor pressure ofless than or equal to 1 Torr at a temperature higher than or equal to−50° C., which is available by the plasma processing apparatus 10.Therefore, as the first example of the processing gas, the C₇F₈ gas andthe C₆F₆ gas can be used. However, the first example of the processinggas is not limited to the C₇F₈ gas and the C₆F₆ gas, and anyfluorocarbon gas having a saturated vapor pressure of less than or equalto 1 Torr at a stage temperature may be used as the first example of theprocessing gas.

A second example of the processing gas is a hydrocarbon gas (i.e.C_(X)H_(Y) gas), or an oxygen-containing hydrocarbon gas (i.e.C_(X)H_(Y)O_(Z) gas), where X, Y, Z are an integer larger than or equalto 1. As the second example of the processing gas, benzene (C₆H₆),n-butanol (CH₃(CH₂)₂CH₂OH), 2-butoxy ethanol (CH₃(CH₂)₃OCH₂CH₂OH),2-ethoxy ethanol (C₂H₅OCH₂CH₂OH), cyclohexane (C₆H₁₂), dioxane(OCH₂CH₂OCH₂CH₂), ethanol (C₂H₅OH), ethyl acetate (CH₃CO₂C₂H₅), ethylbenzene (C₂H₅C₆H₅), ethyl cyclohexane (C₆H₁₁C₂H₅), methyl ethyl ketone(C₂H₅COCH₃), n-octane (CH₃(CH2)₆CH₃), 1-propanol (CH₃CH₂CH₂OH),2-propanol ((CH₃)₂CHOH), and toluene (C₆H₅CH₃) are exemplified.

FIG. 11 is a graph illustrating a relationship between a saturated vaporpressure of the second example of the processing gas and the temperatureof the stage PD. In FIG. 11, a relationship between saturated vaporpressures (a vertical axis; unit: Torr) of methanol, ethanol, and2-propanol as the second example of the processing gas, and thetemperature of the stage PD (a horizontal axis; unit: ° C.) isillustrated. As illustrated in FIG. 11, the processing gas of the secondexample also has a saturated vapor pressure of less than or equal to 1Torr at a temperature higher than or equal to −50° C., which isavailable by the plasma processing apparatus 10.

The second example of the processing gas may be a processing gas inwhich the number of oxygen atoms in molecules included in the processinggas is less than or equal to ½ of the number of carbon atoms in themolecules. As such a second example of the processing gas, a gas otherthan methanol among the gases exemplified above may be used. Accordingto the processing gas having such an atomic ratio, it is possible toreduce damage of the porous film PL caused by oxygen.

In Step ST1 of one embodiment, the first gas is supplied into theprocessing chamber 12 such that the partial pressure of the processinggas becomes greater than or equal to 20% and less than or equal to 100%of the saturated vapor pressure of the processing gas at the temperatureof the stage PD. In addition, in Step ST1, the pressure of the space inthe processing chamber 12 is set to a pressure of less than or equal to1 Torr, that is, 133.3 Pa (Pa). Furthermore, the partial pressure of theprocessing gas in Step ST1, the temperature of the stage PD, and thepressure of the space in the processing chamber 12 are set to suitablevalues from the numerical value range described above depending on thetype of the processing gas in order to fill the pores of the porous filmPL with the liquid. According to Step ST1, the processing gas enters inthe pores of the porous film PL from the top surface of the porous filmPL, and the processing gas entering in the pores is liquefied in thepores by the capillary condensation and becomes the liquid.

In addition, the pressure of the space in the processing chamber 12 ofStep ST1 is set to a pressure of less than or equal to 1 Torr, and thusa difference between the pressure of the space in the processing chamber12 of Step ST3 and the pressure of the space in the processing chamber12 of Step ST1 decreases. Therefore, it is possible to shorten the timerequired for changing the first gas to the second gas and for changing apressure at the time of the transition from Step ST1 to Step ST3. Thatis, it is possible to shorten the time required for Step ST2. As aresult thereof, it is possible to reduce the amount of the liquid in theporous film PL which is vaporized in Step ST2.

When combustible gas such as the second example of the processing gas isused as the processing gas in Step ST1, it is necessary to ensure safetyby diluting the processing gas with a large amount of a dilute gas suchas N₂ gas to set the concentration of the processing gas in the firstgas to below an explosion limit concentration. In addition, when a highpressure condition is used in Step ST1, it is necessary to exhaust alarge amount of the first gas at the time of performing Step ST2, andthus it is necessary to exhaust a large amount of the dilute gas.However, by setting the pressure of the space in the processing chamber12 of Step ST1 to a pressure of less than or equal to 1 Torr, it ispossible to reduce the amount of the dilute gas, and the total amount ofthe first gas.

In another embodiment, the second example of the processing gas is usedin Step ST1, and the first gas is supplied into the processing chamber12 such that the partial pressure of the processing gas becomes greaterthan 100% of the saturated vapor pressure of the processing gas at thetemperature of the stage PD. In addition, in Step ST1 of thisembodiment, the pressure of the space in the processing chamber 12 isset to a pressure of less than or equal to 50 mTorr (6.666 Pa). Theprocessing gas supplied at such a partial pressure can be liquefied notonly in the pores of the porous film PL but also in the processingchamber 12. However, since the pressure in the processing chamber 12 isset to a low pressure of less than or equal to 50 mTorr, the number ofmolecules of the processing gas existing in the processing chamber 12 inStep ST1 is small. Therefore, it is possible to fill the pores of theporous film PL with the liquid generated by liquefaction of theprocessing gas while restricting the liquid from non-uniformly adheringto the surface of the porous film PL to form a micromask.

Hereinafter, experimental examples for evaluating the method MT will bedescribed. It should be noted that the disclosure is not limited tothese examples.

Experimental Example 1

In Experimental Example 1, a SiOC film (hereinafter, referred to as a“porous film 1”) which was formed by a spin film forming method, and aSiOC film (hereinafter, referred to as a “porous film 2”) which wasformed by a CVD method were prepared. Then, the pressure of the space inthe processing chamber 12 was set to a variable parameter, and Step ST1was performed. In Step ST1, a gas comprised of C₆F₆ gas was used as thefirst gas. In addition, a flow rate of the first gas in Step ST1 was setto 30 sccm, and the temperature of the stage PD was set to −50° C.

In Experimental Example 1, a refractive index of each of the porous film1 and the porous film 2 after performing Step ST1 was obtained. In FIG.12, the refractive indices obtained in Experimental Example 1 areillustrated. In FIG. 12, a horizontal axis indicates the pressure of thespace in the processing chamber 12 at the time of performing Step ST1,and a vertical axis indicates the refractive index. The refractive indexof the porous film in a state where the pores of the porous film arefilled with the liquid is increased further than the refractive index ofthe porous film in a state where the pores are not filled with theliquid. Referring to the graph illustrated in FIG. 12, particularly inthe porous film 1, when the pressure is greater than or equal toapproximately 6 Pa, it is found that the refractive index is saturatedat a high level. The pressure of 6 Pa is approximately 20% of thesaturated vapor pressure of the C₆F₆ gas at −50° C., which is 27 Pa.Therefore, as the result of Experimental Example 1, it has beenconfirmed that when the processing gas is supplied into the processingchamber at the partial pressure greater than or equal to 20%, theprocessing gas in the pores of the porous film can be liquefied.

Experimental Example 2 and Experimental Example 3

In Experimental Example 2 and Experimental Example 3, a SiOC film (i.e.porous film) formed by a spin film forming method was prepared. Then,the method MT was performed under the following conditions. In addition,in Comparative Experimental Example 1, only the same step as Step ST3 ofExperimental Example 2 was applied to the same porous film as that inExperimental Example 2 and Experimental Example 3. Furthermore, theobject to be processed including the porous film after performing StepST3 was transferred to another processing chamber connected to theplasma processing apparatus used for performing Step ST1 to Step ST3through the vacuum transfer system, and the treatment of Step ST4 wasperformed in the process chamber.

Conditions of Experimental Example 2

-   -   First Gas in Step ST1: C₆F₆ gas (50 sccm)    -   Pressure in Processing chamber 12 in Step ST1: 0.1 Torr (13.33        Pa)    -   Temperature of Stage PD in Step ST1: −50° C.    -   Processing Time in Step ST1: 30 seconds    -   Second Gas in Step ST2: NF₃/SiF₄/Ar gas (100/120/30 sccm)    -   Pressure in Processing chamber 12 in Step ST2: 0.1 Torr (13.33        Pa)    -   Temperature of stage PD in Step ST2: −50° C.    -   Processing Time in Step ST2: 10 seconds    -   Second Gas in Step ST3: NF₃/SiF₄/Ar gas (120/100/30 sccm)    -   Pressure in Processing chamber 12 in Step ST3: 0.1 Torr (13.33        Pa)    -   Temperature of Stage PD in Step ST3: −50° C.    -   High Frequency Power in Step ST3: 60 MHz, 100 W    -   High Frequency Bias Power in Step ST3: 0.4 MHz, 50 W    -   Processing Time in Step ST3: 3 seconds Number of Times of        Performing Sequence SQ: 15 times    -   Temperature of Stage in Step ST4: 200° C.    -   Processing Time in Step ST4: 60 seconds

Conditions of Experimental Example 3

-   -   First Gas in Step ST1: 2-propanol (50 sccm)    -   Pressure in Processing chamber 12 in Step ST1: 0.14 Torr (18.67        Pa)    -   Temperature of Stage PD in Step ST1: −20° C.    -   Processing Time in Step ST1: 30 seconds    -   Second Gas in Step ST2: NF₃/SiF₄/Ar gas (120/100/30 sccm)    -   Pressure in Processing chamber 12 in Step ST2: 0.1 Torr (13.33        Pa)    -   Temperature of Stage PD in Step ST2: −20° C.    -   Processing Time in Step ST2: 5 seconds    -   Second Gas in Step ST3: NF₃/SiF₄/Ar gas (120/100/30 sccm)    -   Pressure in Processing chamber 12 in Step ST3: 0.1 Torr (13.33        Pa)    -   Temperature of Stage PD in Step ST3: −20° C.    -   High Frequency Power in Step ST3: 60 MHz, 100 W    -   High Frequency Bias Power in Step ST3: 0.4 MHz, 50 W    -   Processing Time in Step ST3: 3 seconds    -   Number of Times of Performing Sequence SQ: 15 times    -   Temperature of Stage in Step ST4: 200° C.    -   Processing Time in Step ST4: 60 seconds

In Experimental Examples 2 and 3, the porous film after performing themethod MT was analyzed by using a Fourier transform infraredspectrophotometer (FTIR). In FIG. 13A, spectra which are respectiveresults of the FTIR analysis of the initial porous films (i.e. theporous film in a state prior to the processing of Experimental Example2), the porous film in a state after the processing of ExperimentalExample 2, and the porous film in a state after the processing ofComparative Experimental Example 1 are illustrated. In addition, in FIG.13B, spectra which are respective results of the FTIR analysis of theinitial porous films (i.e. the porous film in a state prior to theprocessing of Experimental Example 3) and the porous film in a stateafter the processing of Experimental Example 3 are illustrated. Asillustrated in FIG. 13A, the spectrum of the porous film in a stateafter the processing of Comparative Experimental Example 1 wasconsiderably different from the spectrum of the initial porous film.That is, it was confirmed that when the etching of Step ST3 wasperformed without performing Step ST1, the porous film was damaged. Onthe other hand, as illustrated in FIG. 13A, the spectrum of the porousfilm in a state after the processing of Experimental Example 2 wasapproximately identical to the spectrum of the initial porous film. Inaddition, as illustrated in FIG. 13B, the spectrum of the porous film ina state after the processing of Experimental Example 3 was approximatelyidentical to the spectrum of the initial porous film. Therefore, it hasbeen confirmed that filling the pores of the porous film with the liquidby using the capillary condensation in Step ST1 as in ExperimentalExample 2 and Experimental Example 3 reduces damage of the porous filmdue to the etching of Step ST3.

Various embodiments have been described, but the aforementionedembodiments are not limiting, and various modifications are conceivable.For example, in the embodiments described above, the plasma processingapparatus 10 is used for performing the method MT, but the method MT maybe performed by using any plasma processing apparatus such as aninductive coupling plasma processing apparatus, or a plasma processingapparatus for generating a plasma by a surface wave such as a microwave.

1. A method of etching a porous film, comprising: supplying a first gasinto a processing chamber of a plasma processing apparatus in which anobject to be processed including the porous film is accommodated; andgenerating a plasma of a second gas for etching the porous film in theprocessing chamber, wherein the first gas is a processing gas having asaturated vapor pressure of less than or equal to 133.3 Pa at atemperature of a stage on which the object is mounted in the processingchamber, or includes the processing gas, and wherein in said supplyingthe first gas, no plasma is generated, and a partial pressure of theprocessing gas supplied into the processing chamber is greater than orequal to 20% of the saturated vapor pressure.
 2. The method according toclaim 1, wherein a sequence including said supplying the first gas andsaid generating the plasma of the second gas is repeatedly performed. 3.The method according to claim 1, further comprising: supplying thesecond gas into the processing chamber without generating the plasmabetween said supplying the first gas and said generating the plasma ofthe second gas.
 4. The method according to claim 1, wherein a pressureof a space within the processing chamber in said supplying the first gasis less than or equal to 133.3 Pa.
 5. The method according to claim 1,wherein a pressure of a space within the processing chamber in saidgenerating the plasma of the second gas is less than or equal to 40 Pa.6. The method according to claim 1, wherein the processing gas includesa fluorocarbon gas.
 7. The method according to claim 1, wherein theprocessing gas includes at least one of C₇F₈ gas and C₆F₆ gas, andwherein in said supplying the first gas, the partial pressure of theprocessing gas which is supplied into the processing chamber is lessthan or equal to 100% of the saturated vapor pressure.
 8. The methodaccording to claim 1, wherein the processing gas is a hydrocarbon gas oran oxygen-containing hydrocarbon gas.
 9. The method according to claim8, wherein the number of oxygen atoms in molecules included in theprocessing gas is less than or equal to ½ of the number of carbon atomsin the molecules.
 10. The method according to claim 1, furthercomprising: exhausting a gas generated by vaporizing a liquid which isgenerated from the processing gas and exists in the porous film.